Acyl-aryl disazo having a 6-ureido-1-hydroxy-naphthalene-3-sulfonic acid coupling component

ABSTRACT

Anionic disazo dyes useful for dyeing and printing textile materials, paper and leather and for the preparation of inks of the formula ##STR1## wherein D, R 3 , R 4 , M, R 5  and R 7  are defined as in the specification.

This is a continuation of Ser. No. 07/492,247, filed Mar. 9, 1990, nowabandoned, which in turn is a continuation of Ser. No. 07/182,612, filedApr. 18, 1988, now abandoned.

The present invention relates to anionic disazo dyes of formula ##STR2##wherein D is a radical of formula ##STR3##

X is --COOM or --SO₃ M

R¹ and R² are each independently of the other hydrogen, C₁ -C₄ alkyl orC₁ -C₄ alkoxy,

m is 0, 1 or 2,

n is 0 or 1, and

m+n are 1 or 2, with the proviso that two sulfo groups present in thesame ring may not be in ortho-position to each other,

R³ is hydrogen, C₁ -C₄ alkyl or C₁ -C₄ alkoxy,

R⁴ is hydrogen or C₁ -C₄ alkyl, with the proviso that the twosubstituents R³ and R⁴ are in para-position to each other if they have ameaning different from hydrogen,

R⁵ is hydrogen, C₁ -C₄ alkyl or a radical ##STR4## R⁶ and R⁸ are eachindependently of the other hydrogen or C₁ -C₂ alkyl, with the provisothat one substituent R⁶ and one substituent R⁸ must be hydrogen,

R⁷ is hydrogen, C₅ -C₇ cycloalkyl, C₁ -C₆ alkyl which is unsubstitutedor substituted by amino, C₁ -C₄ alkylamino or C₁ -C₄ dialkylamino, aradical of formula ##STR5## or a radial of formula --A--Y, R⁹ ishydrogen or C₁ -C₄ alkyl,

A is the direct bond or a straight chain or branched C₁ -C₆ alkyleneradical,

Y is phenyl or naphthyl, each unsubstituted or substituted by sulfo,carboxy, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkoxycarbonyl orC₁ -C₄ hydroxyalkoxycarbonyl, or

R⁵ and R⁷, together with the linking nitrogen atom, are a pyrrolidine,piperidine or morpholine radical or a piperazine radical which isunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl or C₁-C₄ aminoalkyl at the nitrogen atom which is not attached to thetriazine ring,

p and q are each independently of the other 0 or a whole number notgreater than 3, and

M is hydrogen or the equivalent of a colourless cation.

X in the radical of formula (a) is preferably the sulfo group.

R¹ and R² as alkyl are, for example, methyl, ethyl, n-propyl, isopropyl,n-butyl or tert-butyl. R¹ and R² as alkoxy are, for example, methoxy,ethoxy, or butoxy.

R¹ is preferably hydrogen, methyl, methoxy or ethoxy, in particularhydrogen, methyl or methoxy and, most preferably, hydrogen or methyl.

R² is preferably hydrogen or methyl and, most preferably, hydrogen.

If R¹ and R² are hydrogen, the substituent X may be in ortho-, meta- orpara-position to the azo group.

If the radical of formula (a) contains a further substituent in additionto the substituent X, then X and R¹ or R² are preferably inmeta-position to each other, i.e. preferably in positions 2 and 4 to theazo group. The substituent X is also preferably in 3-, 5- or 4-positionto the azo group and R¹ or R³ is in ortho- or para-position to thesubstituent X, i.e. X and R¹ or R² are preferably in 2,5- or3,4-position to the azo group.

If the radical of formula (a) contains two further substituents inaddition to the substituent X, then X is preferably in position 4 or 5and the two substituents R¹ and R² are in positions 2,5 and 2,4respectively to the azo group.

If D is a radical of formula (b), then two sulfo groups present in thesame ring cannot be in ortho-position to each other. A sulfo grouppresent in the radical of formula (b) is, for example, in positions 5,6, 7 or 8, preferably in positions 5 and 6. If the radical of formula(b) is substituted by two sulfo groups, these are, for example, inpositions 3,6, 3,7, 4,8, 5,7 or 6,8, preferably in positions 3,6, 4,8and 6,8.

D is preferably a radical of formula (a).

Alkyl or alkoxy groups R³ and/or R⁴ are, for example, the groups citedfor R¹ and R². Preferably R³ and R⁴ are each independently of the otherhydrogen, methyl, methoxy or ethoxy and, most preferably, are eachhydrogen. R⁵ is preferably methyl, ethyl, --CH₂ --CH₂ --OH or, mostpreferably, hydrogen.

R⁶, R⁸ and R⁹ are preferably each independently of one another methylor, most preferably, hydrogen.

p and q are each preferably 1 and, most preferably, 0.

R⁵ and R⁷, together with the linking nitrogen atom, can also form apiperidine, morpholine or piperazine radical. The piperazine radical canbe substituted by C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl or C₁ -C₄ aminoalkylat the nitrogen atom which is not attached to the triazine ring. Thepreferred substituent is hydroxyethyl.

The preferred meanings of R⁷ are methyl, ethyl, hydroxyethyl,aminoethyl, each unsubstituted or mono- or dialkylated at the N-atom byC₁ -C₄ alkyl, or a group of formula --(CH₂ --CH₂ --O)_(p) --CH₂ --CH₂--OH, where p is 0 or 1, or a group --A--Y, in which A and Y are asdefined for formula (1).

A as a straight chain or branched C₁ -C₆ alkylene radical is, forexample, methylene, ethylene, ethylidene, propylene, trimethylene,ethylethylene, 1-methyl-1,3-trimethylene. The preferred meaning of A ismethylene or ethylene. Of particular interest, however, are thecompounds of formula (1), wherein A is the direct bond, i.e. those inwhich the phenyl or naphthyl radical is attached direct to the N-atom.

Examples of suitable substituents of the phenyl and naphthyl radical aresulfo, carboxy, methyl, ethyl, methoxy, ethoxy, chlorine,methoxycarbonyl, ethoxycarbonyl or hydroxyethoxycarbonyl.

Preferably Y is a naphthyl radical which carries one or two sulfogroups, or is a phenyl radical which is unsubstituted or substituted bysulfo, carboxy, chlorine, methyl, methoxy, ethoxy, ethoxycarbonyl orhydroxyethoxycarbonyl.

Particularly preferred compounds of formula (1) are those in which Y isan unsubstituted phenyl radical or a phenyl radical which is substitutedby sulfo or carboxy.

M is hydrogen or the equivalent of a colourless anion, for example,lithium, sodium, potassium, ammonium or the protonated form of a C₄ -C₁₂trialkylamine, C₄ -C₁₂ diamine or C₂ -C₁₂ alkanolamine.

M as a protonated C₄ -C₁₂ trialkylamine may be, for example, protonatedN-ethyldimethylamine, N,N-diethylmethylamine, tri-n-propylamine,tri-n-butylamine, triisobutylamine and, in particular, triethylamine ortriisopropylamine. Mixtures of different protonated amines are alsosuitable.

M as a protonated C₄ -C₁₂ diamine is, for example, an ethylenediamine or1,3-diaminopropane in which one or both N-atoms are additionallysubstituted by one or two C₁ -C₄ alkyl radicals, preferably by methyl orethyl groups. M is in this case preferably a N,N-dialkylethylenediamineor N,N-dialkyl-1,3-diaminopropane, for example, N-ethylethylenediamine,N,N-dimethylethylenediamine, N,N'-dimethylethylenediamine,N,N-diethylethylenediamine, 3-dimethylamino-1-propylamine or3-diethylamino-1-propylamine.

M as a protonated C₂ -C₁₂ alkanolamine may be, for example, theprotonated form of a monoalkanolamine, dialkanolamine,monoalkanolmonoalkylamine, monoalkanoldialkylamine, dialkanolalkylamineor trialkanolamine, or a mixture of different protonated alkanolamines.Examples are protonated 2-aminoethanol, bis(2-hydroxyethyl)amine,N-(2-hydroxyethyl)methylamine, N-(2-hydroxyethyl)dimethylamine,N-(2-hydroxyethyl)diethylamine, N-N-bis(2-hydroxyethyl)methylamine,N,N-bis(2-hydroxyethyl)ethylamine or tris(2-hydroxyethyl)amine,2-(2-aminoethoxy)ethanol or diethylaminopropanol.

The preferred meaning of M is N.sup.⊕, Li.sup.⊕ or protonated C₄ -C₆alkanolamine, tris(2-hydroxyethyl)amine, bis(2-hydroxyethyl)amine or amixture of these two amines being the preferred C₄ -C₆ alkanolamines.

A particularly preferred embodiment of the invention comprises thedisazo dyes of formula ##STR6## wherein R¹ and R² are each independentlyof the other hydrogen, C₁ -C₄ alkyl or C₁ -C₄ alkoxy,

R³ is hydrogen, C₁ -C₄ alkyl or C₁ -C₄ alkoxy,

R⁴ is hydrogen or C₁ -C₄ alkyl, with the proviso that the twosubstituents R³ and R⁴ are in para-position to each other if they have ameaning different from hydrogen,

R⁵ is hydrogen, methyl, ethyl or a radical ##STR7## R⁶ is hydrogen or C₁-C₂ alkyl, R⁸ is hydrogen, sulfo or carboxy,

R⁹ is hydrogen or C₁ -C₄ alkyl,

R¹⁰ is hydrogen, sulfo, carboxy, chlorine, methoxy, ethoxy,ethoxycarbonyl or hydroxyethoxycarbonyl,

_(p) is 0 or 1, and

M is hydrogen or the equivalent of a colourless cation.

Among these compounds, those compounds are especially preferred in whichR¹ is hydrogen, methyl or methoxy, R² is hydrogen or methyl, R³ and R⁴are each independently of the other hydrogen, methyl, methoxy or ethoxy,R⁵ is hydrogen or hydroxyethyl, R⁸ is hydrogen, sulfo or carboxy, R⁹ andR¹⁰ are each hydrogen and M is Na.sup.⊕, Li.sup.⊕ or protonated C₄ -C₆alkanolamine.

The disazo dyes of formula (1) are prepared in a manner known per se,for example by reacting a compound of formula ##STR8## wherein Q is anunsubstituted or substituted phenyl or alkyl radical, with an amine offormula ##STR9## with either the compound of formula (3) or the reactionproduct of the compound (3) and the amine of formula (4) being coupledwith a diazotised amine of formula ##STR10## in which formulae (4) and(5) above the substituents R⁵, R⁷, D, R³ and R⁴ are as defined forformula (1).

The disazo dyes of formula (1) can also be prepared by reacting I-acid(7-amino-4-hydroxy-2-naphthalenesulfonic acid) with an isocyanate offormula

    OCN--A--Y'                                                 (6)

to give a compound of formula ##STR11## and coupling said compound offormula (7) to a diazotised amine of formula (5), in which formulaeabove Y' is phenyl or naphthyl, each unsubstituted or substituted bysulfo, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄ alkoxycarbonyl.

A further means of preparing the disazo dyes of formula (1) comprisesfirst coupling I-acid with a diazotised amine of formula (5) and thenacylating the reaction product with an isocyanate of formula (6).

It is preferred first to couple a compound of formula (3) with adiazotised amine of formula (5) and then to react the resultant disazocompound with an amine of formula (4), which reactions are carried outwithout isolation of the intermediates, or to react I-acid with anisocyanate of formula (6) and then to react the reaction product with anamine of formula (5).

The compounds of formulae (3), (4), (5) and (6) are known or can beprepared in known manner.

The coupling reaction is also carried out in a manner known per se, forexample in the temperature range from 0° to 75° C., preferably from 0°to 35° C., and at a pH in the range from 5 to 9.

The reaction of the compound of formula (3), or of the disazo compoundobtained from the compound of formula (3) and the diazotised amine offormula (5) with an amine of formula (4), is likewise carried out in amanner known per se, for example in the temperature range from 30° to100° C. in aqueous solution and in the pH range from 7 to 9.

The reaction of I-acid, or of the coupling product of I-acid and adiazotised amine of formula (5), with an isocyanate of formula (6) isalso carried out in a manner known per se.

The resultant compounds of formula (1) can be isolated in a manner knownper se, e.g. by salting them out.

The colourless cation M can likewise be introduced by known methods, forexample via the dye acid, by ion pair extraction or by membranetechnology.

The novel compounds of formula (1) are preferably used as dyes fordyeing and printing textile materials, paper, leather, and for thepreparation of inks.

If the azo dyes of the present invention are used for dyeing andprinting textile materials, then suitable materials are in particularthose made of cotton. The novel dyes have good affinity for thesetextile materials, a good degree of exhaustion and good build-up. Theygive red dyeings of good fastness properties, in particular goodwetfastness and lightfastness properties.

The preferred utility of the novel dyes of formula (1) is for dyeing andprinting paper of all kinds, especially bleached and sized lignin-freepaper.

The dyes of formula (1) exhaust well on to these substrates, and thewastewater--even when dyeing in deep shades (up to greater than 1/1standard depth dyeing)--remains almost colourless, which is anoutstanding technical and environmental advantage. The good degree ofexhaustion is also advantageous for a good reproducibility of shade. Thedyeings are wetfast, i.e. they exhibit no tendency to bleeding when dyedpaper in the wet state is brought into contact with moist white paper.This property is particularly desirable for tissues, of which it can beexpected that the dyed paper in the wet state (e.g. impregnated withwater, alcohol, surfactant solution and the like) will come into contactwith other substrates such as textiles, paper and the like, which haveto be protected against soiling. If desired, a cationic fixing agent canalso be used when dyeing paper with the dyes of this invention.

The red dyeings are brilliant in shade and have very good fastnessproperties, especially lightfastness.

Further, the dyes of formula (1) are used for dyeing leather materialsby a very wide range of application methods such as spraying, brushingand immersing, and for the preparation of inks of all kinds, such as forball-point pens and printing inks.

The invention is illustrated by the following non-limitative Examples,in which parts and percentages are by weight.

EXAMPLE 1

To 6.9 parts of the phenyl carbamate of formula ##STR12## (obtained byacylating I-acid with phenyl chloroformate and coupling to diazotised4-amino-1,1'-azobenzene-4'-sulfonic acid) in 50 parts of water are added2 parts of metanilic acid. The reaction mixture is adjusted with sodiumhydroxide solution to pH 7.5 and stirred at 60° C. until no morestarting material can be detected by thin-layer chromatography. Theresultant dye of formula ##STR13## is isolated as sodium salt by saltingout with NaCl. It dyes paper in brilliant bluish red shades. Thetinctorial properties such as lightfastness, fastness to bleeding andaffinity for paper, are excellent. The filter cake can be processeddirect to liquid formulations.

The same dye with comparably good properties is obtained by replacing inthis Example the 6.9 parts of phenyl carbamate by corresponding amountsof ethyl, isobutyl or benzyl carbamate and carrying out the processunder the same reaction conditions.

EXAMPLE 2

40 parts of the urea compound of formula ##STR14## (obtained byacylating I-acid with phenyl isocyanate in known manner) are charged to500 parts of water and coupled with 27 parts of diazotised4-amino-1,1'-azobenzene-4'-sulfonic acid at 0°-5° C. The pH is keptbetween 6 and 7 with 2N sodium hydroxode solution. The dye of formula##STR15## is then salted out with NaCl. It dyes paper in shades similarto those obtained with the dye described in Example 1.

EXAMPLES 3-59

The dyes listed in the following Table are obtained by proceduresanalogous to those described in the foregoing Examples. ##STR16##

                                      TABLE                                       __________________________________________________________________________    Ex.                                                                              R.sub.1      R.sub.2              Shade on paper                           __________________________________________________________________________                     ##STR17##           bluish red                               4                                                                                 ##STR18##                                                                                  ##STR19##           bluish red                               5                                                                                 ##STR20##                                                                                  ##STR21##           bluish red                               6                                                                                 ##STR22##                                                                                  ##STR23##           bluish red                               7                                                                                 ##STR24##                                                                                  ##STR25##           bluish red                               8                                                                                 ##STR26##                                                                                  ##STR27##           bluish red                               9                                                                                 ##STR28##                                                                                  ##STR29##           bluish red                               10                                                                                ##STR30##                                                                                  ##STR31##           bluish red                               11                                                                                ##STR32##                                                                                  ##STR33##           bluish red                               12                                                                                ##STR34##                                                                                  ##STR35##           bluish red                               13                                                                                ##STR36##                                                                                  ##STR37##           bluish red                               14                                                                                ##STR38##                                                                                  ##STR39##           bluish red                               15                                                                                ##STR40##                                                                                  ##STR41##           bluish red                               16                                                                                ##STR42##                                                                                  ##STR43##           bluish red                               17                                                                                ##STR44##                                                                                  ##STR45##           bluish red                               18                                                                                ##STR46##                                                                                  ##STR47##           bluish red                               19                                                                                ##STR48##                                                                                  ##STR49##           bluish red                               20                                                                                ##STR50##                                                                                  ##STR51##           bluish red                               21                                                                                ##STR52##                                                                                  ##STR53##           bluish red                               22                                                                                ##STR54##                                                                                  ##STR55##           bluish red                               23                                                                                ##STR56##                                                                                  ##STR57##           bluish red                               24                                                                                ##STR58##                                                                                  ##STR59##           bluish red                               25                                                                                ##STR60##                                                                                  ##STR61##           bluish red                               26                                                                                ##STR62##                                                                                  ##STR63##           bluish red                               27                                                                                ##STR64##                                                                                  ##STR65##           bluish red                               28                                                                                ##STR66##                                                                                  ##STR67##           bluish red                               29                                                                                ##STR68##                                                                                  ##STR69##           bluish red                               30                                                                                ##STR70##                                                                                  ##STR71##           bluish red                               31                                                                                ##STR72##                                                                                  ##STR73##           red                                      32                                                                                ##STR74##                                                                                  ##STR75##           red                                      33                                                                                ##STR76##   NHCH.sub.2 CH.sub.2 OH                                                                             red                                      34                                                                                ##STR77##                                                                                  ##STR78##           red                                      35                                                                                ##STR79##                                                                                  ##STR80##           red                                      36                                                                                ##STR81##                                                                                  ##STR82##           red                                      37                                                                                ##STR83##                                                                                  ##STR84##           red                                      38                                                                                ##STR85##                                                                                  ##STR86##           red                                      39                                                                                ##STR87##                                                                                  ##STR88##           red                                      40                                                                                ##STR89##   NHCH.sub.2 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                     red                                      41                                                                                ##STR90##   NHCH.sub.2 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                              red                                      42                                                                                ##STR91##                                                                                  ##STR92##           red                                      43                                                                                ##STR93##   NHCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          red                                      44                                                                                ##STR94##   NHCH.sub.3           red                                      45                                                                                ##STR95##   NHC.sub.2 H.sub.5    red                                      46                                                                                ##STR96##   NHC.sub.4 H.sub.9    red                                      47                                                                                ##STR97##   N(CH.sub.3).sub.2    red                                      48                                                                                ##STR98##   N(C.sub.2 H.sub.5).sub.2                                                                           red                                      49                                                                                ##STR99##                                                                                  ##STR100##          bluish red                               50                                                                                ##STR101##                                                                                 ##STR102##          bluish red                               51                                                                                ##STR103##                                                                                 ##STR104##          bluish red                               52                                                                                ##STR105##                                                                                 ##STR106##          bluish red                               53                                                                                ##STR107##                                                                                 ##STR108##          bluish red                               54                                                                                ##STR109##                                                                                 ##STR110##          bluish red                               55                                                                                ##STR111##                                                                                 ##STR112##          bluish red                               56                                                                                ##STR113##                                                                                 ##STR114##          bluish red                               57                                                                                ##STR115##                                                                                 ##STR116##          bluish red                               58                                                                                ##STR117##                                                                                 ##STR118##          bluish red                               59                                                                                ##STR119##                                                                                 ##STR120##          bluish red                               __________________________________________________________________________

EXAMPLE 60

200 parts of the dye of Example 2 are homogenised in the form of thefree dye acid of low salt content by stirring in 500 parts of water anddissolved at 40° C. by addition of 58 parts of diethanolamine and 100parts of urea. The solution is clarified by filtration by adding afilter aid. The filtrate is allowed to cool to room temperature and madeup to 1000 parts with water, to give a stable dye solution whichconstitutes a liquid commercial form.

Instead of using diethanolamine it is also possible to usemonoethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, thepolyglycolamines disclosed in German Offenlegungsschrift 2 061 760,ammonia, tetramethylammonium hydroxide, lithium hydroxide or lithiumcarbonate.

EXAMPLE 61

70 parts of chemically bleached softwood sulfite pulp and 30 parts ofchemically bleached birchwood sulfite pulp are beaten in 2000 parts ofwater in a hollander. To this pulp are added 2.5 parts of the dyesolution described in Example 60. After mixing for 20 minutes, paper isprepared from this pulp. The absorbent paper so obtained is dyed red.The wastewater is almost colourless.

EXAMPLE 62

0.5 part of the dye powder of Example 1 is dissolved in 100 parts of hotwater and the solution is cooled to room temperature. This solution isadded to 100 parts of chemically bleached sulfite pulp which has beenbeaten in 2000 parts of water in a hollander. After mixing thoroughlyfor 15 minutes, sizing is effected in conventional manner with rosinsize and aluminium sulfate. Paper prepared from this pulp is dyed in ared shade of good fastness properties.

EXAMPLE 63

69 g of the dyestuff sodium salt obtained in Example 2 are stirred in600 ml of water and then 160 ml of nitrobenzene, 40.7 g of tributylamineand 22 ml of 32% HCl are added at 50° C. The batch is stirred at 70° C.until the dye has completely transferred to the organic phase. Theaqueous phase is discarded and the organic phase is washed with 2×600 mlof hot water. Then 250 ml of water and 39.7 g of triethanolamine areadded and the mixture is stirred at 85° C. until the dye has transferredcompletely to the aqueous phase. The aqueous phase is freed from tracesof nitrobenzene and tributylamine by steam distillation, to give astable dye solution. The organic phase is used as obtained for furtherextractions.

What is claimed is:
 1. A disazo dye of the formula ##STR121## wherein Yis unsubstituted phenyl and M is a colourless cation.
 2. A disazo dye ofthe formula ##STR122## wherein R³ is hydrogen or C₁ -C₄ alkyl,Y isunsubstituted phenyl or phenyl which is substituted by sulfo, C₁ -C₄alkyl, carboxy, Cl, C₁ -C₄ alkoxy, ethoxycarbonyl orhydroxyethoxycarbonyl and M is a colourless cation.
 3. A disazo dye ofthe formula ##STR123## wherein R³ is hydrogen or methyl,Y isunsubstituted phenyl or phenyl which is substituted by sulfo, C₁ -C₄alkyl, carboxy, Cl, C₁ -C₄ alkoxy, ethoxycarbonyl orhydroxyethoxycarbonyl and M is a colourless cation.
 4. A disazo dye ofthe formula ##STR124## wherein R³ is hydrogen or C₁ -C₄ alkyl,Y isunsubstituted phenyl and M is a colourless cation.
 5. A disazo dye ofthe formula ##STR125## wherein R³ is hydrogen or methyl,Y isunsubstituted phenyl and M is a colourless cation.